JP2007271937A - Photosensitive black composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive black composition having high light shielding effect, high stability and excellent adhesion to a glass substrate, and also to provide a color filter with a black matrix having high light shielding effect. <P>SOLUTION: The photosensitive black composition contains (a) carbon black, (b) a photopolymerization initiator, (c) a dye derivative, (d) a resin and (e) an ethylenically unsaturated compound, wherein the ethylenically unsaturated compound (e) contains a carboxyl group-containing compound (C) prepared by reacting a compound (A) having a specific structure with a compound (B) having a functional group to react with an acid anhydride group and an unsaturated double bond. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive black composition used for forming a black matrix constituting a color filter used in a liquid crystal display device or an image pickup tube element, and a color including a black matrix formed from the photosensitive black composition. Regarding filters.

The color filter forms a grid-like black pattern called a black matrix (hereinafter sometimes abbreviated as “BM”) between red (R), green (G), and blue (B) filter segments. Is common. The function of this black matrix is to block the light from the backlight and improve the contrast, and to prevent color mixing of adjacent RGB pixels.
In the black matrix formation method, a metal thin film is formed on a transparent substrate using a metal compound such as chromium by vapor deposition or sputtering, and then a fine pattern is formed through a photolithography method and an etching process (metal) BM), and a method (resin BM) formed by a photolithography method using a photosensitive black composition in which a black component such as carbon black is dispersed in a photosensitive material has been developed.

However, the metal BM is not only very expensive to manufacture due to the complicated manufacturing process, but it is difficult to form it on a large substrate from the viewpoint of apparatus cost or from a technical point of view because it employs a vapor deposition method or a sputtering method. In addition, commonly used chromium is not preferred in terms of environmental issues.
In recent years, the resin BM has attracted attention in place of the metal BM from the viewpoint of the environmental problems described above and also from the viewpoint of cost reduction. The resin BM has a problem that the light shielding property (optical density = OD) is lower than that of the metal BM. That is, the metal BM can generally obtain a desired light-shielding property with a film thickness of 0.1 to 0.2 μm, while the resin BM has a film thickness of 1 to 1 in order to exhibit an equivalent light-shielding property. Must be set to 2 μm. When creating a color filter, in order to eliminate light leakage, the BM and the adjacent RGB layer are overlapped and formed, but in the resin BM, the step where the BM and the RGB layer overlap is increased. Causes a problem that the liquid crystal alignment is disturbed and the display quality is deteriorated. Against this background, the resin BM is required to have a high light shielding property, that is, a high OD value per unit film thickness.

  Therefore, attempts have been made to increase the content of light-shielding components such as carbon black contained in the composition in order to improve the light-shielding property of the black matrix and reduce the level difference. However, in the method of increasing the content of the light-shielding component, in addition to the decrease in adhesion and sensitivity to the glass substrate, developability, resolution, black matrix pattern shape and composition stability (sensitivity change over time) , Development property change, resolution change, and pattern shape change) are deteriorated.

For example, Patent Documents 1 to 3 disclose a photosensitive black composition using a compound having a specific skeleton, which is related to the stability of the photosensitive black composition (sensitivity change over time and pattern shape). Change), high light-shielding properties and adhesion to the glass substrate at the same time, and further from the viewpoint of cost, it was still insufficient.
JP 2002-088136 A Japanese Patent No. 2020553 Japanese Patent No. 3184293

  An object of the present invention is to provide a photosensitive black composition incorporating (e) an ethylenically unsaturated compound having a specific structure. It is another object of the present invention to provide a color filter having a black matrix that optimizes the composition of the photosensitive black composition and has a high light-shielding property, stability, and excellent adhesion to a glass substrate.

（式中、Ｒ１およびＲ２は、それぞれ独立に、酸無水物基を含有する１価の有機残基を表す。Ｒ３およびＲ４は、それぞれ独立に、水素原子もしくは１価の有機残基を表す。ただし、Ｒ１およびＲ３、またはＲ２およびＲ４は、それぞれが一体となって環を形成しても良い。） The present invention is a photosensitive black composition comprising (a) carbon black, (b) a photopolymerization initiator, (c) a dye derivative, (d) a resin, and (e) an ethylenically unsaturated compound. (e) an ethylenically unsaturated compound (A) represented by the following general formula (1), a compound (B) having a functional group capable of reacting with an acid anhydride group and an unsaturated double bond; It contains the carboxyl group containing compound (C) formed by making this react.

(In the formula, R 1 and R 2 each independently represent a monovalent organic residue containing an acid anhydride group. R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic residue. However, R1 and R3, or R2 and R4 may be combined to form a ring.)

（式中、Ｒ_１およびＲ_２は、それぞれ独立に、酸無水物基を含有する１価の有機残基を表す。Ｒ_３およびＲ_４は、それぞれ独立に、水素原子もしくは１価の有機残基を表す。ただし、Ｒ１およびＲ３、またはＲ２およびＲ４は、それぞれが一体となって環を形成しても良い。） Next, the present invention provides a photosensitive black composition comprising (a) carbon black, (b) a photopolymerization initiator, (c) a dye derivative, (d) a resin, and (e) an ethylenically unsaturated compound. In the product, (e) an ethylenically unsaturated compound having a compound (A) represented by the following general formula (1), a functional group capable of reacting with an acid anhydride group and an unsaturated double bond ( A compound (D) obtained by reacting a carboxyl group-containing photosensitive compound (C) obtained by reacting with B) with a compound (G) having a functional group capable of reacting with a functional group contained in the compound (C). It is related with the photosensitive black composition characterized by doing.

(Wherein R ₁ and R ₂ each independently represent a monovalent organic residue containing an acid anhydride group. R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent organic residue. (However, R1 and R3, or R2 and R4 may be combined to form a ring.)

Further, (a) carbon black has an average primary particle diameter of 20 to 40 nm, specific surface area 70~180m ² / g, and the above photosensitive black composition is preferably less carbon black oil absorption 100 cm ^3/100 g.
(B) The above photosensitive black composition, wherein the photopolymerization initiator is at least one photopolymerization initiator selected from an oxime photopolymerization initiator, an imidazole photopolymerization initiator, and a borate photopolymerization initiator. Is preferred.
Furthermore, said photosensitive black composition containing a polyfunctional thiol is preferable.

（式中、Ｑは有機色素残基を、Ｘは直接結合、−ＣＯＮＨ−Ｙ₂−、−ＳＯ₂ＮＨ−Ｙ₂−または−ＣＨ₂ＮＨＣＯＣＨ₂ＮＨ−Ｙ₂−（但し、Ｙ₂は置換基を有してもよいアルキレン基またはアリール基を表す。）を、Ｙ₁は−ＮＨ−または−Ｏ−を、Ｚは水酸基、アルコキシ基、下記一般式（３）で示される置換基またはｎが１の場合には−ＮＨ−Ｘ−Ｑを、Ｒ₁およびＲ₂は、それぞれ独立に置換もしくは無置換のアルキル基またはＲ₁およびＲ₂とで形成される少なくとも窒素原子を含むヘテロ環を、ｍは１から６の整数を、ｎは１から４の整数を表す。
一般式（３）

（式中、Ｙ₃は−ＮＨ−または−Ｏ−を表す。Ｒ_１、Ｒ_２およびｍは上記一般式（２）における定義と同様である。）） Moreover, (c) The said photosensitive black composition characterized by the pigment derivative containing the pigment derivative shown by following General formula (2) is preferable.
General formula (2)

(Wherein Q is an organic dye residue, X is a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ — or —CH ₂ NHCOCH ₂ NH—Y ₂ — (where Y ₂ is a substituent) Y ₁ represents —NH— or —O—, Z represents a hydroxyl group, an alkoxy group, a substituent represented by the following general formula (3), or n. Is 1 -NH-XQ, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group or a heterocycle containing at least a nitrogen atom formed by R ₁ and R _2. , M represents an integer of 1 to 6, and n represents an integer of 1 to 4.
General formula (3)

(In the formula, Y ₃ represents —NH— or —O—. R ₁ , R ₂ and m are the same as defined in the general formula (2).)

  Next, the present invention relates to a color filter comprising a black matrix formed from the above photosensitive black composition on a transparent substrate.

  The photosensitive black composition of the present invention has high light shielding properties, excellent stability and adhesion to a glass substrate, and is low in cost. Therefore, by using the photosensitive black composition of the present invention, a black matrix having a high light shielding property can be formed at a low cost.

（式中、Ｒ１およびＲ２は、それぞれ独立に、酸無水物基を含有する１価の有機残基を表す。Ｒ３およびＲ４は、それぞれ独立に、水素原子もしくは１価の有機残基を表す。Ｒ１およびＲ３の組み合わせ、またはＲ２およびＲ４の組み合わせは、それぞれが一体となって環を形成しても良い。） The photosensitive black composition of the present invention contains (a) carbon black, (b) a photopolymerization initiator, (c) a dye derivative, (d) a resin, and (e) an ethylenically unsaturated compound. Moreover, the color filter of this invention is equipped with the black matrix formed from the photosensitive black composition of this invention on a transparent substrate.
Furthermore, (e) the ethylenically unsaturated compound is a compound (B) represented by the following general formula (1), a compound having a functional group capable of reacting with an acid anhydride group and an unsaturated double bond (B And a carboxyl group-containing compound (C) obtained by reacting with (A).
Alternatively, (e) the ethylenically unsaturated compound is a compound (B) represented by the following general formula (1), a compound having a functional group capable of reacting with an acid anhydride group and an unsaturated double bond (B A compound (D) obtained by reacting a compound (G) having a functional group capable of reacting with a functional group of the compound (C) into a carboxyl group-containing photosensitive compound (C) obtained by reacting It is characterized by that.

(In the formula, R 1 and R 2 each independently represent a monovalent organic residue containing an acid anhydride group. R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic residue. The combination of R1 and R3, or the combination of R2 and R4 may be combined to form a ring.)

<Compound (A) Represented by General Formula (1)>
Compound (A) has at least two acid anhydride groups as described above. These may be a mixture of two or more.
Here, the monovalent organic residue is an atomic group composed of an aliphatic, aromatic, or heteroatom-containing atomic group alone or in combination, specifically, an acid anhydride group, an alkyl group, a cycloalkyl group. Groups, aliphatic organic groups such as alkyloxy groups, and aromatic organic residues such as aryl groups. These further include halogen atoms, alkyl groups having 1 to 8 carbon atoms, aryl groups, amino groups, cyano groups, You may have substituents, such as an alkoxy group and an alkylthio group.

The compound (A) may be any compound represented by the general formula (1). Specifically, 9,9-Bis (3,4-dicarboxyphenyl) fluorene Dianhydride (R1 and R2 are acid anhydride groups). Yes, R1 and R3, and R2 and R4 are united.)
9,9-Bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene Dianhydride (R1 and R2 are acid anhydrides of a dicarboxyphenoxyphenyl group, and R3 and R4 are hydrogen atoms). Examples thereof include carboxylic acid anhydrides. Of course, these compounds can also be used in combination. In addition, polycarboxylic acids, polycarboxylic acid esters, polycarboxylic acid half esters, and the like that can be converted into anhydrides through a dehydration reaction during the reaction are included in the compounds having an acid anhydride group referred to in the present invention.

  Compound (A) may contain a polycarboxylic dianhydride other than those described above, if necessary. For example, pyromellitic anhydride, phthalic anhydride dimer, benzophenone tetracarboxylic dianhydride, diphenyl ether tetracarboxylic anhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride , Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid" by Shin Nippon Rika Co., Ltd. "MTA-10", "Licacid MTA-15", "Licacid TMEG series", "Licacid TDA" etc. can be used together.

<Compound (B) having a functional group capable of reacting with an acid anhydride group and an unsaturated double bond>
Examples of the functional group capable of reacting with the acid anhydride group include a hydroxyl group, a glycidyl group, and an amino group, and a hydroxyl group is particularly preferable from the viewpoint of easy control of the reaction.
As unsaturated double bond, (meth) acryloyl group, vinyl group, vinyloxy group, allyl group, (meth) acryloylphenyl group, vinylphenyl group, vinyloxyphenyl group, allylphenyl group, maleic acid group, itaconic acid group Etc. In order to increase the exposure sensitivity by the active energy ray, the number of unsaturated double bonds is preferably 3 or more.

A known compound can be used as the compound having a hydroxyl group and three or more unsaturated double bonds.
Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

In addition, as a compound having a functional group capable of reacting with an acid anhydride group and two or less unsaturated double bonds,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyl Roxyethyl-2-hydroxyethyl-phthalic acid, glycerol mono (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dihydroxy acrylate, glycerol (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (Meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol diacrylate, isocyan Such as Le acid EO-modified diacrylate.

<Carboxyl group-containing photosensitive compound (C)>
The compound (C) is obtained by reacting the acid anhydride group of the compound (A), the functional group capable of reacting with the acid anhydride group, and the functional group of the compound (B) having an unsaturated double bond. It is. The reaction between an anhydride group and a functional group capable of reacting with the anhydride group easily reacts under well-known conditions. In this case, the molar equivalent ratio of the anhydride group to the functional group is used in the range of 5: 1 to 1: 5, but 1: 1 is preferable.

<Compound (D)>
The compound (D) is obtained by reacting the carboxyl group or hydroxyl group of the compound (C) with the carboxyl group or hydroxyl group of the compound (G).

<Compound (G) having functional group capable of reacting with functional group of compound (C)>
The compound (G) has a functional group that can react with a functional group in the structure of the compound (C). In particular, it reacts with a carboxyl group or a hydroxyl group in the compound (C).
Examples of the functional group capable of reacting with a carboxyl group include an epoxy group, an oxazoline group, an amino group, a carbodiimide group, an isocyanato group, and an isothiocyanate group.
Examples of the functional group capable of reacting with a hydroxyl group include an isocyanato group, an acid halide, an acid anhydride group, and a carboxyl group.
An epoxy group is particularly useful as a functional group capable of reacting with a carboxyl group.

  The reaction for obtaining the compound (D) may be performed without a solvent, or may be performed in a solvent inert to the reaction. Examples of the solvent include hydrocarbon solvents such as n-hexane, benzene and toluene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, diethyl ether, tetrahydrofuran or Ether solvents such as dioxane, halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazo Examples include polar solvents such as lysinone. Two or more of these solvents may be used in combination.

  In addition, when a reaction with an acid halide of (meth) acrylic acid is performed, hydrogen halide (for example, hydrogen chloride) is by-produced. For example, triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, Organic bases such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), or sodium bicarbonate, sodium carbonate Inorganic bases such as potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide may be used as the dehydrochlorinating agent.

  Hereinafter, the compound (G) is further reacted with the compound (E) having a functional group capable of reacting with the functional group of the compound (C) and a polymerizable double bond, and the functional group of the compound (C). The description will be divided into the compound (F) having a functional group that can be obtained and having no polymerizable double bond.

<Compound (E)>
The compound (E) is characterized by having a functional group capable of reacting with the functional group of the compound (C) and a polymerizable double bond.
A well-known thing can be used as a compound which has an epoxy group and a polymerizable double bond. For example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) Examples include acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, glycidyl cinnamate, 1,3-butadiene monoepoxide, Celoxide 2000 (manufactured by Daicel Chemical Industries, Ltd.), and the like.
Examples of the compound having a functional group capable of reacting with a hydroxyl group and a polymerizable double bond include methacryloyloxyethyl isocyanate (MOI), vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate (MAI), isopropenyl-α, α- Examples include dimethylbenzyl isocyanate (TMI). 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group or amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.
Or the acid halide of (meth) acrylic acid, halopropionic acids, or these acid halides etc. are mentioned. When halopropionic acids or acid halides thereof are used, the produced halopropionic acid ester compound can be dehydrohalogenated to produce a (meth) acrylic acid ester compound.

<Compound (F)>
The compound (F) has a functional group capable of reacting with the functional group of the compound (C) and does not have a polymerizable double bond.
A well-known thing can be used as a compound which has an epoxy group and does not have a polymerizable double bond. For example, those containing a halogen atom other than aromatic, sulfur atom, phosphorus P atom, and fluorine can be used. Specifically, styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, m-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, Phenol (EO) 5 Glycylyl Ether, p-tert-Butylphenyl Glycidyl Ether, Lauryl Alcohol (EO) 15 Glycidyl Ether, Glycidyl Ether of a mixture of C11-C15 Alcohol (Denakol EX-192 made by Nagase ChemteX Corporation), N-Glycylyl Phyllide thritol Polyglycyl Ether, polycondensate of α-hydroxyphenyl-ω-hydropoly (n = 1-7) (biphenyldimethylene-hydroxyphenylene) and 1-chloro-2,3-epoxypropane (manufactured by Nippon Kayaku Co., Ltd.) NC-3000) bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, and the like.

A well-known thing can be used as a compound which has a functional group which can react with a hydroxyl group, and does not have a polymerizable double bond. For example, monoisocyanate can be mentioned. Examples of the monoisocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, and phenyl isocyanate.
In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate, and equimolar amounts of hydroxyl group, carboxyl group, and amide group-containing compounds without unsaturated double bonds The compound reacted with can also be used as an isocyanate compound.

<Catalyst>
A catalyst is preferably used for the reaction for obtaining the compound (D).
For example, when the reaction between the carboxyl group and the epoxy group proceeds, a catalyst such as amines may be added as necessary. As the catalyst used, a known catalyst can be used. Examples of the catalyst include the following compounds (I) to (V).

(I) Tertiary amines and / or salts thereof Triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methylpiperazine, etc. (II) Imidazoles and / or salts thereof 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl- (1 )]-Ethyl-S-triazine, etc. (III) Diazabicyclo compounds 1,5-diazabicyclo [5.4.0] -7-undecane, 1,5-diazabicyclo [4.3.0] -5-nonene, 1 , 4-diabicyclo [2.2.2] octane, etc. (IV) Phosphines Tributylphosphine, Riphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine, etc. (V) Phosphonium salts Tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate etc

  The compounding ratio of the compound having an epoxy group and the catalyst used in the present invention is 0.01 to 10 parts by weight of the catalyst with respect to 100 parts by weight of the compound having an epoxy group. If the catalyst is less than 0.01 parts by weight, the reaction is slow, and if it exceeds 10 parts by weight, the water resistance of the cured product may be lowered.

  When the softening temperature of the compound having an epoxy group to be used is lower than the reaction temperature range, the reaction between the carboxyl group and the epoxy group can be carried out without a solvent. Moreover, it can also carry out using a suitable solvent irrespective of the softening temperature of the compound which has an epoxy group to be used. The solvent to be used can be used without particular limitation as long as it does not react with an epoxy group, a hydroxyl group or an organic acid. For example, known solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, acetone, and benzene can be used.

The ethylenically unsaturated compound other than those described above contained in the photosensitive black composition of the present invention may have one or more ethylenically unsaturated double bonds, and may be a monomer, oligomer, or photosensitizer. Can be used.
Examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tris. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
Examples of the oligomer include epoxy (meth) acrylate, urethane (meth) acrylate, and ester (meth) acrylate.

  Furthermore, as a photosensitive resin, the photosensitive resin which introduce | transduced the ethylenically unsaturated bond to the below-mentioned resin by a well-known method can be used. For example, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group present in the resin, A resin obtained by reacting cinnamic acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified product can be used.

Said ethylenically unsaturated compound is used individually by 1 type or in mixture of 2 or more types.
The ethylenically unsaturated compound is preferably 5 to 30% by weight based on the total solid weight of the photosensitive black composition (100% by weight), more preferably 7 to 28% from the viewpoint of photocurability and developability. %, Particularly preferably in an amount of 10 to 25% by weight. When the content of the ethylenically unsaturated compound is more than 30% by weight, it is not preferable because the black matrix pattern shape is poor in linearity and cross-sectional shape. Since curability is insufficient, it is not preferable.

  The resin (d) of the present invention is particularly limited as long as it is soluble in a developer used in the development processing step, particularly preferably an alkali developer, when forming a pattern. Not but, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic Resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, celluloses, thermoplastic resins such as polyethylene, polybutadiene, polyimide resin, epoxy resin, benzoguanamine resin, rosin modified maleic acid resin, rosin modified Fumaric acid resin, melamine resin, urea resin, pheno It may be used in combination with a thermosetting resin such as a resin. Preferably, an alkali-soluble resin that is a carboxyl group-containing copolymer can be used, and further, a variety of resins can be selected based on low cost viewpoints, ease of synthesis, and ease of resin modification. From the viewpoints of dispersibility of carbon black and storage stability of the composition, it is preferable to use an acrylic resin having one or more carboxyl groups.

  In the photosensitive black composition of the present invention, the ratio (M / P) of the weight (P) of the resin (d) to the weight (M) of the ethylenically unsaturated compound (e) is 0.10 to 0.70. It is preferable that it is 0.15-0.65, and it is especially preferable that it is 0.20-0.60. When M / P is less than 0.10, the sensitivity is low, and when M / P exceeds 0.70, the black matrix pattern shape is poor in linearity, cross-sectional shape, or tack.

The photosensitive black composition of the present invention contains (a) carbon black as a light shielding component.
(a) carbon black has an average primary particle diameter of 20 to 40 nm, specific surface area 70~180m ² / g, oil absorption of 100 cm ^3/100 g can be preferably used the following carbon black. The oil absorption of the present invention refers to the oil absorption of dibutyl phthalate.
A photosensitive black composition using carbon black having an average primary particle diameter of less than 20 nm is advantageous from the viewpoint of light shielding properties due to the large number of carbon black particles per unit volume. Is inferior. Furthermore, it is difficult to stably disperse carbon black, and there is a problem of causing a phenomenon of residue (or also called background stain) in which a part of the black composition remains on the glass substrate after development.

  On the other hand, in the photosensitive black composition containing carbon black having an average primary particle diameter of more than 40 nm, the number of carbon black particles per unit volume is small and photocurability is advantageous. In particular, the linearity is insufficient.

When carbon black with a specific surface area of less than 70 m ² / g is used, it tends to cause deterioration of the pattern shape and adhesion of the black matrix, and when carbon black greater than 180 m ² / g is used, the stability of the carbon black Dispersion becomes difficult.

Oil absorption of carbon black is preferably from the viewpoint of photocuring is 100 cm ^3/100 g or less, more preferably 0~80cm ³ / 100g, particularly preferably 0~50cm ³ / 100g.

The average primary particle diameter of 20 to 40 nm, as the specific surface area 70~180m ² / g, oil absorption of 100 cm ^3/100 g in which carbon black or less, for example, CABOT made MOGUL L, BLACK PEARLS (L, 520,450,430) , REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99R, 99I), MA manufactured by Mitsubishi Chemical (77, 7, 8, 11, 100, 100R, 100S, 200RB, 14), # (52, 50, 47, 45, 45L, 44, 33, 32, 95, 85, 260), CF9, Special Black550 manufactured by DEGUSSA, Printex (55, 45, 300, ES23, 35), 350, manufactured by Asahi Carbon Asahi # 70L N-326, RAVE made by Columbian Carbon (1255, 1250, 1200, 1170, 1040, 1035, 1030, 1020, 1000, 890 POWDER, 890H POEDER, 850), etc., preferably REGAL (250R, 250) manufactured by CABOT, manufactured by Mitsubishi Chemical # 47, Particularly preferably, REGAL (250R, 250) manufactured by CABOT can be used.

  On the other hand, for the purpose of improving the light-shielding property of the black matrix, two types of light-shielding materials are used in combination to increase the light-shielding property (OD value), that is, carbon black having a small average particle size and carbon having a large average particle size. It has been proposed to improve the OD value by forming a close-packed structure in a black matrix in combination with black (for example, JP-A-9-133806 and JP-A-9-279082). (Kaihei 11-80584). Similarly, in the photosensitive black composition of the present invention, it is possible to employ a technique for increasing the OD value by using two types of carbon black together.

In the photosensitive black composition of the present invention, when two or more types of carbon black are used in combination to increase the OD value, the difference in average primary particle diameter is 5 nm or more as a light shielding component, and (a1) average primary particles It contains carbon black having a diameter of 8 to 20 nm and (a2) carbon black having an average primary particle diameter of 21 to 40 nm, and does not contain carbon black exceeding 40 nm.
A photosensitive black composition using carbon black (a1) having an average primary particle size of 8 to 20 nm alone is advantageous in terms of light shielding properties because it has a large number of carbon black particles per unit volume, but has high light shielding properties. Therefore, the photocurability is inferior. In addition, it is difficult to stably disperse carbon black, and there is a problem that a phenomenon of a residue (or also referred to as background stain) is caused in which a part of the black composition remains on the glass substrate after development.

On the other hand, in the photosensitive black composition using carbon black (a2) having an average primary particle diameter of 21 to 40 nm alone, the number of carbon black particles per unit volume is small and the photocurability is advantageous, but the light shielding property. Is insufficient.
Further, in the photosensitive black composition containing carbon black having an average primary particle diameter exceeding 40 nm, the number of carbon black particles per unit volume is small and photocurability is advantageous, but the light shielding property and the pattern shape of the black matrix, In particular, the linearity is insufficient.

As the carbon black (a1), those having an average primary particle diameter of 10 to 18 nm are preferable, and carbon black having a specific surface area of 200 to 600 m ² / g can be suitably used. When carbon black with a specific surface area of less than 200 m ² / g is used, it tends to cause deterioration of the pattern shape and adhesion of the black matrix, and when carbon black of more than 600 m ² / g is used, the stability of the carbon black Dispersion becomes difficult. Carbon black having an average primary particle diameter of less than 8 nm is difficult to produce, and is not suitable as carbon black (a1).

Further, as the carbon black (a2), those having an average primary particle diameter of 22 to 37 nm are preferable, and carbon black having a specific surface area of 40 to 600 m ² / g can be suitably used. When carbon black with a specific surface area of less than 40 m ² / g is used, it tends to cause deterioration of the pattern shape and adhesion of the black matrix, and when carbon black greater than 600 m ² / g is used, the stability of the carbon black Dispersion becomes difficult.
Furthermore, when the average primary particle size of carbon black (a1) and carbon black (a2) is less than 5 nm, a high light-shielding effect is expected when carbon black (a1) and carbon black (a2) are used in combination. Can not.

  (a1) Examples of carbon black having an average primary particle size of 8 to 20 nm include MONARCH or BLACK PERLS (1400, 1300, 1100, 1000, 900, 880, 800, 700) manufactured by CABOT, VULCAN (P, 9A32). ), Mitsubishi Chemical # (2700B, 2650, 2600, 2450B, 2400B, 2350, 2300, 1000, 990, 980, 970, 960, 950, 900, 850), MCF88, MA600, Color Black (FW2000, manufactured by CEGUSSA) , FW2, FW2V, FW1, FW18, S170, S160), Special Black (6, 5), Printex (95, 90, 85, 80, 75, 40, 60), Tokai Carbon Seast (9H SAF-HS, 9 S F), Asahi Carbon's Asahi # 80, Colombian Carbon's ROYAL SPECTRA, NEO SPECTRA MARK (I and II), NEO SPECTRA AG, SUPERBA (NEO MK III), NEO SPECTRA MARK IV, Raven (5000, 7000, 5750, 5250, 3500, 3200, 2000, 1500), CONDUCTEX (40-220, SC), RAVEN C BEADS, and the like. Preferably, MONARCH (1100, 800) manufactured by CABOT, BLACK PERLS (1100, 800), # 850 manufactured by Mitsubishi Chemical, Printex 95 manufactured by DEGUSSA, particularly preferably MONARCH 1100 manufactured by CABOT, and Printex 95 manufactured by DEGUSSA can be used.

(A2) Examples of carbon black having an average primary particle size of 21 to 40 nm include, for example, VULCAN (XC72R, XC72), MOGUL L, BLACK PEARLS (L, 570, 520, 490, 480, 470, 460, manufactured by CABOT, 450, 430, 420, 410), REGAL (660R, 660, 500R, 330R, 330, 300R, 250R, 250, 99R, 99I), ELFTEX (5, 8, 12, PELLETS115), Mitsubishi Chemical MA (77 , 7, 8, 11, 100, 100R, 100S, 230, 200RB, 14), # (750B, 650B, 52, 50, 47, 45, 45L, 44, 40, 33, 32, 30, 95, 85, 260, 3230B, 3350B), CF9, SPE made by DEGUSSA ial Black (4, 4A, 550, 350), Printex (150T, U, V, 140U, 140V, 55, 45, P, L6, L, 300, 30, ES23, 3, ES22, 35, XE2), Tokai Carbon sheet [6ISAF, 600ISAF-LS, 5H-IISAF-HS, KH (N339), 3H HAF-HS, NH (N351), 3 HAF, 3M, NLI-HAF, 300 HAF-LS, 116 MAF] Asahi Carbon, Asahi # 75, Asahi # 70 (-IH, -IN, -L), Asahi HS-500, Asahi F-200, Colombian Carbon RAVEN (1255, 1250, 1200, 1170, 1040, 1035, 1030 BEADS, 1020, 1000, 890 POWDWE, 890 HPOWDER, 850, 82 BEADS), CONDUCTEX (975BEADS, 900BEADS) and the like. Preferably, REGAL (300R, 250R, 250, 99R, 99I) manufactured by CABOT, MA (7, 11, 100R), # (47, 45, 45L) manufactured by Mitsubishi Chemical, Printex55 manufactured by DEGUSSA, particularly preferably Mitsubishi Chemical # 47 manufactured by CABOT and REGAL 250R manufactured by CABOT can be used.

The weight ratio of carbon black (a1) and carbon black (a2) is 3 to 30 parts by weight, preferably 3 to 10 parts by weight, based on 1 part by weight of (a1).
(A1) When (a2) is less than 3 parts by weight relative to 1 part by weight, that is, when (a1) is more, stable dispersion of carbon black becomes difficult. On the other hand, when (a2) exceeds 30 parts by weight relative to 1 part by weight of (a1), that is, when (a1) is further reduced, it appears when carbon black (a1) and (a2) are used in combination. High light blocking effect cannot be expected.
In addition, the carbon black used in the photosensitive black composition of the present invention is based on the total solid weight of the photosensitive black composition (100% by weight), including the case where carbon blacks having different average primary particle sizes are used in combination. As a total amount of 40 to 65% by weight, more preferably 45 to 60% by weight.

  Examples of the photopolymerization initiator (b) contained in the photosensitive coloring composition of the present invention include, for example, an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, a benzophenone photopolymerization initiator, and a thioxanthone photopolymerization initiator. , Triazine photopolymerization initiator, carbazole photopolymerization initiator, imidazole photopolymerization initiator, oxime photopolymerization initiator, borate photopolymerization initiator, phosphine photopolymerization initiator, quinone photopolymerization initiator, A titanocene photopolymerization initiator or the like can be used. Among these, from the viewpoint of photocurability, at least one photopolymerization initiator selected from an oxime photopolymerization initiator, an imidazole photopolymerization initiator, and a borate photopolymerization initiator is preferable, and an oxime photopolymerization initiator is used. Particularly preferred.

Examples of the oxime photopolymerization initiator include etanone represented by the following general formula (14), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O -Acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo) -2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and the like.
Formula (14)

Examples of the imidazole photopolymerization initiator include 2,2′bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole.
Examples of the borate photopolymerization initiator include compounds represented by the following general formulas (15) to (18).

As the acetophenone-based photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like.
Examples of the benzoin photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal.
Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like.

Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and the like.
Examples of the triazine photopolymerization initiator include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s -Triazine, 2,4-bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxy styryl) -6-triazine.

Examples of the phosphine photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the quinone photopolymerization initiator include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.

The said photoinitiator is used individually by 1 type or in mixture of 2 or more types. The photopolymerization initiator can be used in an amount of preferably 0.5 to 50% by weight, more preferably 2 to 20% by weight, based on the total solid content weight of the photosensitive black composition (100% by weight). .
The ratio (I / M) of the weight (I) of the photopolymerization initiator (b) to the weight (M) of the ethylenically unsaturated compound (e) is preferably 0.10 to 1.0. 0.15-0.8 is more preferable, and 0.20-0.6 is particularly preferable. If the I / M is less than 0.10, the sensitivity is low, and if the I / M exceeds 1.00, the pattern width after development with respect to the black matrix pattern shape poor linearity, cross-sectional shape failure or mask pattern width. Problems such as fatness occur.

  The photosensitive black composition of the present invention may contain a sensitizer. Examples of the sensitizer include α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethyliso Examples include phthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like. The said sensitizer can be used individually by 1 type or in mixture of 2 or more types. The sensitizer is preferably used in an amount of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total solid weight of the photosensitive black composition (100% by weight). it can.

The (c) dye derivative contained in the photosensitive black composition of the present invention refers to a compound in which a substituent is introduced into an organic dye. Here, the organic dye refers to a compound including a light yellow aromatic polycyclic compound such as naphthalene type and anthraquinone type which is not generally called a dye, and mainly a compound having a generic name of a color index described later. Say.
As the pigment derivative, those represented by the following general formula (2) can be preferably used. Examples of the dye derivative represented by the general formula (2) include dye derivatives represented by the following general formulas (4) to (13).

（式中、Ｑは有機色素残基、Ｘは直接結合、−ＣＯＮＨ−Ｙ₂−、−ＳＯ₂ＮＨ−Ｙ₂−、
または−ＣＨ₂ＮＨＣＯＣＨ₂ＮＨ−Ｙ₂−（但し、Ｙ₂は置換基を有してもよいアルキレン基またはアリール基を表す。）、Ｙ₁は−ＮＨ−または−Ｏ−、Ｚは水酸基、アルコキシ基、下記一般式（３）で示される置換基、またはｎが１の場合には−ＮＨ−Ｘ−Ｑ、
一般式（３）

（式中、Ｙ₃は−ＮＨ−または−Ｏ−、Ｒ₁およびＲ₂は、それぞれ独立に置換もしくは無置換のアルキル基、またはＲ₁とＲ₂とで形成される少なくとも窒素原子を含むヘテロ環、ｍは１から６の整数、ｎは１から４の整数を表す。） General formula (2)

(Wherein, Q is an organic dye residue, X is a direct bond, -CONH-Y _2- , -SO ₂ NH-Y _2- ,
Or —CH ₂ NHCOCH ₂ NH—Y ₂ — (wherein Y ₂ represents an alkylene group or an aryl group which may have a substituent), Y ₁ represents —NH— or —O—, Z represents a hydroxyl group, An alkoxy group, a substituent represented by the following general formula (3), or —NH—XQ when n is 1,
General formula (3)

Wherein Y ₃ is —NH— or —O—, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, or a hetero atom containing at least a nitrogen atom formed by R ₁ and R _2. Ring, m represents an integer of 1 to 6, and n represents an integer of 1 to 4.)

一般式（２）で示される色素誘導体を構成する有機色素としては、例えば、フタロシアニン系、キナクリドン系、キナクリドンキノン系、イソインドリノン系、キノフタロン系、ジケトピロロピロール系、ペリレン系、ペリノン系、インジゴ系、チオインジゴ系、ジオキサジン系、アントラキノン系、ピランスロン系、アンスアンスロン系、フラバンスロン系、インダンスロン系、金属錯体系等の縮合多環系有機顔料、ベンズイミダゾロン系、不溶性アゾ系、縮合アゾ系、溶性アゾ系等の他の有機顔料または染料が挙げられる。

Examples of the organic dye constituting the dye derivative represented by the general formula (2) include phthalocyanine, quinacridone, quinacridonequinone, isoindolinone, quinophthalone, diketopyrrolopyrrole, perylene, perinone, Indigo, thioindigo, dioxazine, anthraquinone, pyranthrone, anthanthrone, flavanthrone, indanthrone, metal complex, etc. condensed polycyclic organic pigments, benzimidazolone, insoluble azo, condensation Other organic pigments or dyes such as azo-based and soluble azo-based are listed.

  The pigment derivative represented by the general formula (2) may be used alone or in combination of two or more. The pigment derivative represented by the general formula (2) is preferably 0.05 to 20% by weight, more preferably 0.5 to 10% by weight based on the total solid content weight of the photosensitive black composition (100% by weight). % Can be used. When the content of the pigment derivative is less than 0.05% by weight, the effect of dispersing the carbon black is not sufficiently exhibited. When the content is more than 20% by weight, the dispersion of the carbon black becomes unstable, which is not preferable.

The photosensitive black composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimerca DOO -s- triazine, 2-(N, N-dibutylamino) -4,6-dimercapto -s- triazine, trimethylolpropane tris (3-mercapto isobutyrate), and the like. These polyfunctional thiols can be used alone or in combination.

Among these polyfunctional thiols, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), and trimethylolpropane tris (3-mercaptoisobutyrate) can be preferably used.
Moreover, these polyfunctional thiols are preferable when combined with an imidazole-based photopolymerization initiator among the photopolymerization initiators, because the sensitivity is increased and the photocurability is improved.
The polyfunctional thiol can be used in an amount of preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total solid content weight of the photosensitive black composition (100% by weight). If the amount is less than 0.1% by mass, the effect of adding a polyfunctional thiol is insufficient. If the amount exceeds 30% by mass, the sensitivity is too high and the resolution is lowered, and the stability of the photosensitive black composition is lowered.

The photosensitive black composition of the present invention may contain a solvent in order to sufficiently disperse carbon black and form a black matrix having a desired film thickness. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylbenzene, ethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, xylene, ethyl cellosolve, methyl- Examples include n-amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents, and these can be used alone or in combination.
The solvent can be used in an amount of preferably 150 to 3500 parts by weight, more preferably 250 to 2000 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive black composition.

The photosensitive black composition of the present invention may be added with a surfactant, a silane coupling agent, other additives, etc. for the purpose of improving coating properties, improving sensitivity, and improving adhesion. good.
The photosensitive black composition is composed of carbon black, a pigment derivative, an ethylenically unsaturated compound, a photopolymerization initiator, a resin, a solvent, and, if necessary, other additives, a three roll mill, a two roll mill, It can be produced by dispersing using various dispersing devices such as sand mill, kneader, attritor, and micros.
The photosensitive black composition is prepared by means of centrifugal separation, sintering filter, membrane filter, or the like, with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a black matrix formed from the photosensitive black composition of the present invention on a transparent substrate such as a glass plate and at least two color filter segments other than black. The color of the filter segment is selected from about 2 to 6 colors from blue, green, red, cyan, yellow, magenta, orange, purple and the like. Filter segments having the same color system and different densities may be formed.
The black matrix is formed by applying the photosensitive black composition of the present invention on a transparent substrate by a coating method such as spin coating, slit coating, roll coating, etc., and then active energy rays from the composition coating surface side through a photomask. Can be formed by soaking in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove an unirradiated portion, that is, an uncured portion and developing.

The coating thickness of the photosensitive black composition is preferably in the range of 0.2 to 5 μm (when dry), and is in the range of 0.5 to 2 μm, which makes it easy to balance coating properties and light shielding properties. Is more preferable.
Further, the optical density (OD) per 1 μm of the dry thickness of the black matrix is preferably 3.0 or more, particularly preferably 3.5 or more, more preferably 3.8 or more, from the viewpoint of high light shielding properties. It is. The higher the optical density, the better. However, when the active energy ray is ultraviolet light or visible light, it becomes difficult to obtain a cured coating film.

As the alkali developer, an aqueous solution such as sodium carbonate or sodium hydroxide is used, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the exposure sensitivity by active energy rays, after coating and drying the photosensitive black composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After the film is formed, active energy rays can be irradiated from the composition application surface side.

  As the active energy ray, an electron beam, ultraviolet rays, or visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source irradiated from the composition application surface side. Moreover, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet rays and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp or a xenon mercury lamp is often used because it is a point light source and has a stable luminance. The active energy dose irradiated from the composition coated surface side can be set in a timely manner within a range of 5 to 1000 mJ, but is preferably within a range of 20 to 300 mJ that can be easily managed in the process.

Each color filter segment can be formed using a gravure offset printing method, a waterless offset printing method, a silk screen printing method, a photolithography method using a solvent developing type or an alkali developing type colored resist, and transparent coloring material by electrophoresis of colloidal particles. Examples thereof include an electrodeposition method in which electrodeposition is formed on a conductive film, and a transfer method in which a filter segment layer formed in advance on the surface of a transfer base sheet is transferred onto a black matrix substrate.
Since the printing method can be patterned simply by repeating printing and drying, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In the case of producing a color filter by a printing method, it is important to control the fluidity of the ink on the printing press, and the ink viscosity can be adjusted with a dispersant or extender pigment.

  The photolithography method using a solvent development type or alkali development type colored resist is a method in which a colored resist is applied to a transparent substrate on which a black matrix is formed by a coating method such as spin coating, slit coating or roll coating, and then through a photomask. In this method, a UV light exposure is performed, the unexposed portion is washed away with a solvent or an alkali developer to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. This manufacturing method can manufacture a color filter with higher accuracy than the above printing method.

The colored resist is a resist containing a desired colorant instead of carbon black contained in the photosensitive black composition of the present invention, but does not necessarily contain the resin represented by the general formula (1). May be. As the colorant, various colorants having excellent resistance are used. However, it is preferable to use a pigment from the viewpoint of light resistance, heat resistance and solvent resistance, and an organic pigment is used because of its light absorption ability. It is particularly preferable to do this. Specific examples of typical pigments are indicated by color index (CI) numbers.
Examples of yellow colorants include Pigment Yellow 12, 13, 14, 20, 24, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, and 166. 173 and the like.
Examples of the orange colorant include Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and the like.

Examples of red and magenta colorants include Pigment Red 9, 97, 122, 123, 144, 149, 166, 168, 177, 190, 192, 215, 216, 224, 254, 255, and the like.
Examples of the purple colorant include pigment violet 19, 23, 29, 32, 33, 36, 37, and 38.
Examples of blue and cyan colorants include Pigment Blue 15 (15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64, and the like.
Examples of the green colorant include Pigment Green 7, 10, 36, and 47.
These colorants may be used in combination of two or more in order to obtain a desired color.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. Further, the number average molecular weight and the weight average molecular weight are values in terms of polystyrene measured by GPC (gel permeation chromatography).

<Synthesis of ethylenically unsaturated compound e1>
9, 9-Bis (3,4-dicoxyphenyl) fluorene dihydride (manufactured by JFE Chemical Co., Ltd., trade name BPAF) 100.0 g in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 50.7 g, hydroquinone 0.08 g (manufactured by Wako Pure Chemical Industries, Ltd.), and cyclohexanone 100.4 g were charged and heated to 85 ° C. Next, 1.51 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was stirred at 85 ° C. for 5 hours, then Phenyl Glycidyl Ether (Nagase ChemteX Corporation). Product, trade name EX-141) 65.5 g and cyclohexanone 42.1 g are added, and then 1.21 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 6 hours. The reaction was terminated by cooling. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN750, and a weight average molecular weight MW 1,000.

<Synthesis of ethylenically unsaturated compound e2>
9, 9-Bis (3,4-dicoxyphenyl) fluorene dihydride (trade name BPAF, manufactured by JFE Cal, Ltd.) 100.0 g in a four-necked flask equipped with a stirrer, reflux condenser, dry air introduction tube, thermometer, 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 50.7 g, hydroquinone 0.08 g (manufactured by Wako Pure Chemical Industries, Ltd.), and cyclohexanone 100.4 g were charged and heated to 85 ° C. Next, 1.51 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred for 5 hours at 85 ° C., and o-phenylphenol glycidyl ether (Sanko Co., Ltd.). Product name OPP-G) 129.5g, cyclohexanone 84.8g
Then, 1.21 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN960, and a weight average molecular weight MW1,200.

<Synthesis of ethylenically unsaturated compound e3>
9, 9-Bis (3,4-dicoxyphenyl) fluorene dihydride (manufactured by JFE Chemical Co., Ltd., trade name BPAF) 100.0 g in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 200.2 g of pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd., trade name: Biscote # 300), 0.15 g of hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) and 200.1 g of cyclohexanone were charged and the temperature was raised to 85 ° C. Next, 1.50 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours. Glycidyl methacrylate (Dow Chemical Japan Co., Ltd.) 62.0 g) and cyclohexanone 42.4 g were added, and then 2.41 g of dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. did. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN830, and a weight average molecular weight MW2,310.

<Synthesis of ethylenically unsaturated compound e4>
9, 9-Bis (3,4-dicoxyphenyl) fluorene dihydride (manufactured by JFE Chemical Co., Ltd., trade name BPAF) 100.0 g in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 200.2 g of pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd., trade name: Biscote # 300), 0.15 g of hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) and 200.1 g of cyclohexanone were charged and the temperature was raised to 85 ° C. Next, 1.50 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours, then Phenyl Glycidyl Ether (Nagase ChemteX Corporation). Product, trade name EX-141) 65.5 g and cyclohexanone 44.8 g were added, and then 2.41 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, and the mixture was stirred at 85 ° C. for 6 hours. The reaction was terminated by cooling. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN870, and a weight average molecular weight MW2,410.

[Preparation of resin solution]
370 parts of propylene glycol monomethyl ether acetate is put into a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is added dropwise over 1 hour at the same temperature to conduct a polymerization reaction Went.
Methacrylic acid 20.0 parts Methyl methacrylate 10.0 parts n-Butyl methacrylate 35.0 parts 2-Hydroxyethyl methacrylate 15.0 parts 2, 2'-azobisisobutyronitrile 4.0 parts paracumylphenol ethylene oxide modification Acrylate 20.0 parts (“Aronix M-110” manufactured by Toagosei Co., Ltd.)
After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained. The weight average molecular weight (GPC measurement) of the acrylic resin was about 40000. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate so that the non-volatile content was 30% in the previously synthesized resin solution. To prepare a resin solution

[Preparation of carbon black dispersion A]
Carbon black CABOT made REGAL250R (average primary particle diameter 35 nm, specific surface area ^{50 m} 2 / g, oil absorption of 46cm ³ / 100g) 100 parts, was mixed 4 parts of dye derivative, a resin solution 70 parts of the following formula (19), cyclohexanone To a final solid content of 20%. This was dispersed for 2 hours with a paint shaker using glass beads having a diameter of 0.8 mm to prepare a carbon black dispersion A. Dispersion A had a viscosity of 6.69 mPa · s at 25 ° C.
(Formula 19)

[Preparation of carbon black dispersion B]
In the preparation of a carbon black dispersion A, a carbon black, CABOT made REGAL250R (average primary particle diameter 35 nm, specific surface area ^{50 m} 2 / g, oil absorption of 46cm ³ / 100g) 80g and, DEGUSSA made Printex95 (average primary particle diameter of 15nm The carbon black dispersion B was prepared in the same manner as the carbon black dispersion A except that the specific surface area was 250 m ² / g and the oil absorption was 52 g / 100 g. The resulting carbon black dispersion B had a viscosity of 6.27 mPa · s at 25 ° C.

[Preparation of carbon black dispersion C]
In the preparation of a carbon black dispersion A, a carbon black, CABOT made MONARCH120 (average primary particle diameter 75 nm, specific surface area ^{25 m} 2 / g, oil absorption of 72cm ³ / 100g) was changed to 100g adjustment of the carbon black dispersion A The carbon black dispersion C was prepared by performing the same operation as described above. The obtained carbon black dispersion C had a viscosity of 5.88 mPa · s at 25 ° C.

[Examples 1 to 12, Comparative Example 1]
(Adjustment of photosensitive black composition)
The mixture shown in Table 1 was stirred and mixed so as to be uniform, and then filtered through a 2 μm filter to obtain a photosensitive black composition. About the obtained photosensitive black composition, the sensitivity, stability, light-shielding property (OD value per unit film thickness), black matrix pattern shape, and adhesion to glass were evaluated by the following methods. The obtained results are shown in Table 2.
In addition, in evaluation of stability, evaluation of all the Examples and the comparative examples was (circle).

エチレン性不飽和化合物Ｘ：ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）
エチレン性不飽和化合物ｅ１〜ｅ４：上記合成例で合成した化合物。
光重合開始剤Ａ：一般式（１４）で示されるオキシム系光重合開始剤（エタノン、１−[９−エチル−６−(２−メチルベンゾイル)−９Ｈ−カルバゾール−３−イル]−、１−(Ｏ−アセチルオキシム)、チバ・スペシャルティ・ケミカルズ社製「イルガキュア ＯＸＥ０２」）
光重合開始剤Ｂ：２,２'ビス（o−クロロフェニル）−４，５，４',５'−テトラフェニル−１,２'−ビイミダゾール
光重合開始剤Ｃ：一般式（１５）で示されるボレート系光重合開始剤
光重合開始剤Ｄ：２−ベンジル−２−ジメチルアミノ−１−(４−モルフォリノフェニ ル) −ブタノン−１（チバ・スペシャルティ・ケミカルズ社製「イルガキュア ３６９」）
多官能チオール：トリメチロールプロパントリス（３−メルカプトブチレート）
溶剤：シクロヘキサノン

Ethylenically unsaturated compound X: dipentaerythritol hexaacrylate (DPHA)
Ethylenically unsaturated compounds e1 to e4: Compounds synthesized in the above synthesis examples.
Photopolymerization initiator A: an oxime photopolymerization initiator represented by the general formula (14) (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1, -(O-acetyloxime), “Irgacure OXE02” manufactured by Ciba Specialty Chemicals)
Photopolymerization initiator B: 2,2′bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole photopolymerization initiator C: represented by the general formula (15) Borate-based photopolymerization initiator photopolymerization initiator D: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“Irgacure 369” manufactured by Ciba Specialty Chemicals)
Multifunctional thiol: trimethylolpropane tris (3-mercaptobutyrate)
Solvent: cyclohexanone

[sensitivity]
After coating the photosensitive black composition on a 10 cm × 10 cm glass substrate by spin coating, a coating film having a dry film thickness of about 1 μm was prepared by drying at 70 ° C. for 15 minutes, and the film thickness was measured. Thereafter, ultraviolet rays of various exposure amounts (mJ / cm ² ) were exposed through a photomask using an ultrahigh pressure mercury lamp. After developing with an aqueous sodium carbonate solution, the unexposed portion was removed by washing with ion exchange water. The film thickness of the exposed part after development and washing was measured, and the minimum exposure amount (mJ / cm ² ) at which a film thickness of 95% or more with respect to the film thickness before development was obtained was taken as the sensitivity. Sensitivity was evaluated 10~50mJ / cm ² ○, as × a case where more than 50 mJ / cm ^2. In addition, a 10 micrometer mask pattern was used for the photomask, and a striped black matrix pattern was formed.

[Stability]
The stability was evaluated by comparing the development speed immediately after the preparation of the photosensitive black composition and after storage for 7 days at 40 ° C.
(Development speed) After coating the photosensitive black composition on a 10 cm × 10 cm glass substrate by spin coating, a coating film having a dry film thickness of about 1 μm was prepared by drying at 70 ° C. for 15 minutes, and the film thickness was measured. did. This was spray-developed using an aqueous sodium carbonate solution, and the time for the photosensitive black composition to disappear was measured. The measurement time was divided by the measured film thickness, and the time per unit film thickness (seconds / μm) was taken as the development speed. ±
The case where the development speed after storage was within ± 15% of the development speed before storage was evaluated as “◯”, and the case where the speed changed over ± 15% and the speed changed slowly was evaluated as “X”.

[Shading (optical density (OD))]
The photosensitive black composition was applied to a glass substrate in the same manner as in the [sensitivity] evaluation, and after heating at 230 ° C. for 1 hour without performing an exposure step, the film thickness was measured. The optical density (OD) of the photosensitive black composition coated substrate thus obtained was measured with a Macbeth densitometer (gretagmacbeth D200-II), and the measured optical density (OD) was divided by the measured film thickness. The optical density (OD / μm) per unit film thickness was determined.

[shape]
The black matrix pattern shape was evaluated by forming a striped black matrix pattern with an exposure amount of 70 mJ / cm ² in the same manner as the [Sensitivity] evaluation, Or it observed with the electron beam scanning microscope and observed linearity and cross-sectional shape.
(Linearity) Linearity ○ when there is no chipping or jaggedness in the straight line part, linearity △ when jaggedness or chipping is found in a part of the straight line part, and many jaggedness or chipping throughout the straight line part When evaluated, it was evaluated as linearity x.
(Cross-sectional shape) When the cross-sectional shape is perpendicular from the forward taper (the bottom surface that is in contact with the glass is wider than the upper base), the cross-sectional shape ○, the cross-sectional shape is an overhang (the upper base is the surface that contacts the glass) In the case of a width wider than the bottom), it was evaluated as x.

[Adhesion]
(Initial adhesion) The photosensitive black composition was coated on a glass substrate in the same manner as in the [sensitivity] evaluation, exposed at an exposure amount of 250 mJ / cm ² , and then heated at 230 ° C. for 1 hour. A high-performance epoxy rapid-curing adhesive (room temperature 1 hour curing type) is attached to the photosensitive black composition-coated surface of the obtained photosensitive black composition-coated substrate, and a cross-cut adhesion test method according to JIS K5400. The glass adhesion of the coating film was evaluated. Peeling was performed by attaching a high-performance epoxy rapid-curing adhesive (curing type at room temperature for 1 hour) to the head of the M6 bolt, bonding (self-weight) on the grid, heating at 90 ° C. for 5 minutes, and then peeling the bolt by hand. Since the bolt was smaller than the 1 mm × 1 mm × 100 grid, the initial adhesion was expressed by the ratio of the non-peeled area of the coating film to the adhesive area of the bolt.
(Adhesiveness after PCT) The photosensitive black composition was coated on a glass substrate in the same manner as in the [sensitivity] evaluation, exposed at an exposure amount of 250 mJ / cm ² , and then heated at 230 ° C. for 1 hour. A pressure cooker test (PCT) was performed on the obtained photosensitive black composition coated substrate. That is, using EHS-411 manufactured by ESPEC CORP., Conforming to an unsaturated pressure cooker test (USPCT; Unsaturated Press. Test) called HAST (Highly Accelerated Temperature and Humidity Stress Test) standardized in IEC68-2-66. The pressure cooker test was conducted for 5 hours under the conditions of 120 ° C., 2 atm and 100% RH. Thereafter, post-PCT adhesion was evaluated by a test similar to the initial adhesion.
For both initial adhesion and post-PCT adhesion, the adhesion (%) was calculated from the following calculation formula (20), and the calculated results were evaluated in five stages from A to X.

Adhesiveness (%) = (Number of cross sections on adhesive surface−Number of cross sections on bolt film adhesion) × 100 Formula (20)
Number of grids on the bolt bonding surface

Round to the nearest decimal point ◎: 90% ≤ Adhesiveness ≤ 100%
○: 70% ≦ adhesion <90%
Δ: 50% ≦ adhesiveness <70%
×: 20% ≦ adhesiveness <50%
XX: 0% ≦ adhesiveness <20%

  As is apparent from Table 2, Examples 1 to 12 of the present invention are superior to Comparative Example 1 in that they are particularly excellent in adhesion, and are compatible with both high light-shielding properties and stability.

Claims (7)

In a photosensitive black composition comprising (a) carbon black, (b) a photopolymerization initiator, (c) a dye derivative, (d) a resin, and (e) an ethylenically unsaturated compound, (e) ethylene An unsaturated compound reacts a compound (A) represented by the following general formula (1) with a compound (B) having a functional group capable of reacting with an acid anhydride group and an unsaturated double bond. A photosensitive black composition comprising a carboxyl group-containing compound (C).

(Wherein R1 and R2 represent a monovalent organic residue containing an acid anhydride group. R3 and R4 represent a hydrogen atom or a monovalent organic residue, provided that R1 and R3, or R2 And R4 may be combined to form a ring. In a photosensitive black composition comprising (a) carbon black, (b) a photopolymerization initiator, (c) a dye derivative, (d) a resin, and (e) an ethylenically unsaturated compound, (e) ethylene An unsaturated compound reacts a compound (A) represented by the following general formula (1) with a compound (B) having a functional group capable of reacting with an acid anhydride group and an unsaturated double bond. And a carboxyl group-containing photosensitive compound (C) comprising a compound (D) obtained by reacting a compound (G) having a functional group capable of reacting with a functional group of the compound (C). Black composition.

(Wherein R ₁ and R ₂ represent a monovalent organic residue containing an acid anhydride group. R ₃ and R ₄ represent a hydrogen atom or a monovalent organic residue, provided that R 1 and R3, or R2 and R4 may be combined to form a ring.) ^3. The photosensitive material according to claim 1, wherein the carbon black is carbon black having an average primary particle diameter of 20 to 40 nm, a specific surface area of 70 to 180 m ² / g, and an oil absorption of 100 cm 3/100 g or less. Black composition.   (b) The photopolymerization initiator is at least one photopolymerization initiator selected from an oxime photopolymerization initiator, an imidazole photopolymerization initiator, and a borate photopolymerization initiator. The photosensitive black composition as described in any one of 3.   Furthermore, polyfunctional thiol is contained, The photosensitive black composition as described in any one of Claims 1-4 characterized by the above-mentioned. (c) The pigment | dye derivative contains the pigment | dye derivative shown by following General formula (2), The photosensitive black composition as described in any one of Claims 1-5 characterized by the above-mentioned.
General formula (2)

(Wherein Q is an organic dye residue, X is a direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ — or —CH ₂ NHCOCH ₂ NH—Y ₂ — (where Y ₂ is a substituent) Y ₁ represents —NH— or —O—, Z represents a hydroxyl group, an alkoxy group, a substituent represented by the following general formula (3), or n. Is 1 -NH-XQ, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group or a heterocycle containing at least a nitrogen atom formed by R ₁ and R _2. , M represents an integer of 1 to 6, and n represents an integer of 1 to 4.
General formula (3)

(In the formula, Y ₃ represents —NH— or —O—. R ₁ , R ₂ and m are the same as defined in the general formula (2).) A color filter comprising a black matrix formed from the photosensitive black composition according to any one of claims 1 to 6 on a transparent substrate.